Densely Arrayed Cage-Shaped Polymer Topologies Synthesized via Cyclopolymerization of Star-Shaped Macromonomers

This work reports a facile and versatile ring-opening metathesis polymerization of three- and four-armed star-shaped poly­(ε-caprolactone) (PCL) macromonomers bearing a norbornenyl group at each chain end using Grubbs’ third-generation catalyst under diluted condition to obtain graft polymers (GPs) comprising densely arrayed three- and four-armed cage-shaped grafted PCLs (GPCLs) with narrow dispersity (1.19–1.35) and a controllable number of cage repeating units up to 40 (molecular weight: ∼320 000 g mol–1). The GPCLs were characterized using nuclear magnetic resonance spectroscopy, size exclusion chromatography, and matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry. The cyclopolymerization proceeded via repetitive rapid intramolecular reactions to form cage-shaped units followed by slow intermolecular propagation. This synthesis was applicable to star-shaped poly­(l-lactide), poly­(trimethylene carbonate), and poly­(ethylene glycol). Investigating the structure–property relationships regarding crystallization behavior, hydrodynamic diameter, and viscosity revealed that cage-shaped topological side chains reduced the chain dimensions and mobility compared to their linear and cyclic counterparts.